O OH

HO

O OH
O
Organic Chemistry and
Spectroscopy
Topic 10+11

http://ibchem.com/IB/ibsyllabus.htm
“The atoms come together in different order and
position, like the letters, which, though they are few,
yet, by being placed together in different ways, produce OH O
innumerable words.” Epicurus (341-270 B.C.) O OH
HO 1 O

O OH

REVIEW SOURCE

▪ Resource
▪ http://ibchem.com/IB/ibsyllabus.htm

▪ http://www.ibchemninja.com/

2
 Introduction
▪ What is organic chemistry?
▪ The study of all biological molecules, all fossil fuels,
synthetic materials (like nylon) and many industrial
products.

▪ Organic chemistry involves reactions and compounds

containing carbon.

▪ Carbon can undergo catenation, the process by which

many identical atoms are joined together by covalent
bonds, producing straight chain, branched or cyclic
structures.

▪ Compounds that DO NOT contain carbon and are called

inorganic. 3

MMM…Cinnamon
▪ Carbon containing molecule responsible for the
smell of cinnamon.

Cinnamaldehyde

4
 Hydrocarbons
▪ Simplest type of organic compound.
▪ Contains ONLY carbon and hydrogen atoms.
Examples:
▪ Methane (CH4) is natural gas used to heat homes.
▪ Propane (C3H8) is used as a heating fuel.
▪ Chains of 5-12 carbon atoms are found in gasoline
and petroleum oil.
▪ Chains of 20 or more carbon atoms are common in
candles and wax.

Types of Formulas
▪ https://www.youtube.com/watch?
v=rUpjHD7aMRk#t=183
▪ Molecular formula = C4H10
▪ Empirical formula = C2H5

▪ Full structural formula (also called graphic or

displayed formula) =

▪ Condensed structure = CH3CH2CH2CH3

6
 Types of Formulas
▪ Skeletal structure:

Stereochemical Formula
▪ Stereochemical Formula
▪ Dotted line: bond sticking behind the page
▪ Wedged line: bond sticking out of the page

8
 Homologous Series

Alkanes are
aliphatic or
straight-
chain
compounds
Saturated: single covalent bonds

Unsaturated: multiple covalent bonds

Naming Hydrocarbons
▪ Nomenclature
▪ Prefix= # of carbon
atoms in molecule.
▪ Suffix = type of
hydrocarbon:
▪ Alkane
▪ Alkene
▪ Alkyne

10
 Learning Check: Alkanes
• Ex.1 Determine the molecular formula for methane.

Molecular formula = CH4

• Ex.2 Determine the molecular formula of ethane.

Molecular formula = C2H6

11

Learning Check
• Ex.3 Determine the molecular formula of propane.

Molecular formula: C3H8

• Ex. 4 Butane?

Molecular formula: C4H10

12
 What is the pattern?
CH4 Each member of the alkane
C2H6 family differs by one C atom and
two H atoms (an additional CH2 group); this
C3H8
defines the nature of a
C4H10 homologous series.
ect…
The members of a series have similar chemical
properties and there is a gradation in physical
properties (like an increase in boiling points due
to stronger London Dispersion Forces.

13

Alkane Structures
▪ Draw the structural formula and condensed
structural (and skeletal structure for propane
and butane) formula for the following alkane
molecules:
CH4
C2H6
C3H8
C4H10

14
 Alkane Structures

CH CH3CH
4 3

CH3CH2C CH3CH2CH2C
H3 H3

Alkenes
• Ex.1 Determine the formula of ethene.
Molecular formula: C2H4

• Ex.2 Propene?
Molecular formula: C3H6

• Ex.3 Butene?
Molecular formula: C4H8
16
 Alkene Pattern
Ethene C2H4
Propene C3H6
Butene C4H8
ect…
▪ There are ALWAYS twice as many H atoms
as C atoms (constant ratio).

17

Alkynes
• Ex.1 Determine the formula of propyne.
Molecular formula: C3H4

• Ex.2 Butyne?
Molecular Formula: C4H6

• There are ALWAYS twice as many H atoms as

C atoms (constant ratio).

18
Homologous Series in General:
Alcohols for example: CnH2n+1OH
CH3OH• You can have a homologous series of any
C2H5OH functional groups too (alcohols, aldehydes,
ketones, esters, etc) .…homologous does not apply
C3H7OH
to hydrocarbons only.
C4H9OH
ect… • Each member has an additional CH2 for any
homologous series
• The members of a series have similar chemical
properties (due to the same functional group,
which is responsible for their overall
reactivity).
• There is a gradation in physical properties. 19

Homologous Series in General:

Aldehydes for example: CnH2nO
Condensed structures: • Let’s draw the
HCHO (Molecular formula CH2O) structure of these
molecules:
CH3CHO
CH3CH2CHO
CH3CH2CH2CHO

ect…

20
 Aromatic Hydrocarbons
▪ Aromatic is a class of compounds (also called arenes)
that have a cyclic structure (characterized by a benzene
ring).
▪ The German scientist August Kekule proposed a ring
structure for benzene of 6 C atoms and 1 H at each C
with alternating single & double bonds.

or
Benzene
shown with alternating
single & double bonds
21

Benzene
▪ Kekule is said to have visualized the cyclic structure of
benzene in a dream.
▪ X-ray diffraction patterns from crystalline benzene
reveal that all 6 C-C bonds in its molecule have
identical bond lengths of 140 pm.
▪ The C-C bond have a bond order of 1.5 (intermediate in
length between single and double C-C bond lengths).

▪ The electron density is equally distributed; hence the

molecule is planar and symmetrical.

22
 Benzene
▪ The delocalization of the electron clouds makes the
molecule stable.

Benzene
circle represents resonance

23

Phenyl Ring
▪ The phenyl group or ring is a cyclic group of atoms
closely related to benzene.
▪ It can be viewed as a benzene ring, minus a hydrogen,
serving as a functional group (C6H5-)

General structure:
*R represents a C chain/group

▪ Commonly found in many organic compounds, both

natural and synthetic (man made)
24
 Classify each structure as an alkane, alkene,
alkyne or aromatic (arene)

Alkyne

CH
Alkane 3

Alkene Aromatic

25

Properties of Hydrocarbons
▪ All organic molecules contain covalent bonds
(electrons are shared!).

▪ DO NOT dissociate into ions in water.

▪ Poor conductors (non-electrolytes).
▪ Hydrocarbons are generally nonpolar molecules.
▪ The attractions BETWEEN molecules are weak
London dispersion forces.

26
 Physical Properties Hydrocarbons
Alkane Boiling Point ( ̊ C)
Methane, CH4 -164
Ethane, C2H6 -89 Gases at room
Propane, C3H8 -42 temp.
Butane, C4H10 -0.5
Liquids at
Pentane, C5H12 36
room temp.
Hexane, C6H14 69
The boiling point increases as their relative molecular
mass increases (London Dispersion forces increase).
With increasing number of carbon atoms are density
and viscosity. 27

Distillation
Physical separation process that
uses different boiling points to
separate a mixture

28
 Crude oil, which can be refined and separated by distillation
into useful substances
Fraction Number of Carbon Use
Atoms

Refinery gas 1-4 Used as fuel on site or cooking

fuel and as a feedstock for
petrochemicals

Gasoline/Naphtha 5-10 Gasoline(petrol) is used as fuel

for cars. Naphtha is used as
chemical feedstock

Kerosene 10-16 Fuel for jets. Paraffin heating

(ex. electric space heaters)

Gas Oil 13-25 Fuel for diesel engines, power

plants and heating

Residue >25 Oil-fired power stations,

polishing waxes, lubricating
oils.

Volatility and Solubility

(Physical Properties) Page:
▪ Volatility is a measure of the tendency of a substance
to vaporize or a measure of how readily a substance
vaporizes.
▪ Volatility depends on the strength of IMFs.

▪ 3 Factors to Consider:
▪ Molecular Polarity
▪ Molecular Mass
▪ Molecular Structure

30
 Volatility and Solubility
(Physical Properties) Page:
▪ Volatility
▪ This is a measure of how easily the substance changes into
the gaseous state.
▪ High volatility means that compound evaporates easily (low
boiling point).
▪ Recall: the longer the carbon chain (greater molecular
mass) the stronger the London Dispersion forces and
the higher the boiling point.

31

Volatility and Solubility

(Physical Properties)
▪ Branching of the carbon chain has an effect on
volatility because it influences the strength of
intermolecular forces.
▪ Branched molecules have less contact with each other than
straight chain isomers and thus, have weaker intermolecular
forces and lower boiling points.
▪ The presence of a functional group will influence
volatility.
▪ Polar groups experience dipole-dipole intermolecular forces
and have higher boiling points.
▪ Groups which can form hydrogen bonds will have even
higher boiling points.

32
 IUPAC Naming System
▪ Rules for naming Alkanes
1. Each compound is named by finding the
LONGEST CONTINUOUS chain of
carbon atoms. The chain DOES NOT have
to appear as a straight chain.
▪ Ex. If the longest chain has 6 carbon atoms in it,
the parent name for the compound is hexane.

33

IUPAC Naming for Alkanes

1. Identify the group attached to the parent chain.
Groups of carbon atom branching off the parent
chain are called alkyl groups (substituents).
▪ An alkyl group contains 1 less H than its
corresponding alkane. The name of the group
corresponds to the alkane prefix:

–CH3 methyl group, –C2H5 ethyl, –C3H7 propyl, ect..

▪ Any hydrocarbon that contains a halogen
substituent, such as –fluoro, –chloro, –iodo or –
bromo is called an alkyl halide.
34
 IUPAC Naming for Alkanes
1. Number the continuous chain of carbon
atoms in the direction that places the
substituent group on the LOWEST-
NUMBERED carbon atom.

35

IUPAC Naming for Alkanes

4. The name(s) of the substituent group(s) and location
number is written FIRST.
▪ The parent name is the LAST part of the name.
▪ A hyphen separates the location number of group
and group name (ex. 2-methyl).
▪ If two substituents are identical the prefix “di” is
added to the name. “Tri” indicates 3 and “tetra”
means 4.
▪ List names of alkyl substituent's in alphabetical
order. (Ex. An ethyl group would be written
before a methyl group).

36
 Example #1
▪ Name the following structure according to
IUPAC rules: On the 2nd
C atom, there is
a -methyl group

5 4 3 2 1

2-methylpentane
37

Ex.2 & Ex.3

Ex.2 Ex.3
3 2 1

2-fluoro-2-methylpropane
2,2-dimethylbutane

38
 Ex.4 & Ex.5
Ex.4 Ex.5

2-methlypropane 2,2,4-trimethlypentane

39

IUPAC Naming for Alkanes

Draw the structures for the following compounds:
• 1,2-dichloropropane
• 2,5-dimethylhexane
• 3-ethyl-2-methylhexane

Name the following:

• CH3CH3
• CH3CH2CHCH3CH2CH3

40
 41

IUPAC for Alkenes & Alkynes

1. The parent chain is the longest continuous C chain
that contains the double or triple bond.
▪ Naming alkyl groups is the same as for alkanes.
2. The parent chain has the ending –ene for alkenes
and –yne for alkynes.
3. The parent chain is numbered to give the double
or triple bond the lowest possible number.
4. A number indicating the position of the double or
triple is inserted JUST BEFORE the parent chain
or just before the –ene or –yne.

42
 Alkene & Alkyne Examples:

2 3
1

Propene
Condensed Structure: CH2CHCH3
Skeletal structure:

43

Alkene & Alkyne Examples:

1 2 3 4

but-1-yne
or 1-butyne

Condensed:
CHCCH2CH3

44
 Name the following structure:

5 4 3 2 1

2-methylpent-2-ene
Location of Location of double bond
substituent

45

IUPAC for Alkenes & Alkynes

▪ Draw structures for the following compounds:
▪ Ethyne
▪ Pent-2-ene
▪ 3-chlorobut-1-ene
▪ Hex-2-yne
▪ 3-ethylhex-1-ene

46
 47

Isomers
▪ C atoms can be linked together in straight chains
(aliphatic), chains with branches, or cyclic
structures.
▪ Isomerism is one reason why there are millions of
organic compounds.

cyclohexane
propane
2-methylpropane
48
 Isomers
▪ Isomers are compounds that have THE SAME
molecular formula, but DIFFERENT structural
formulas (different arrangement of atoms).

▪ Structural isomers may have similar chemical

properties (as in 2-methylpentane and 3-
methylpentane)
▪ Sometimes they can differ in chemical properties if the
atoms are arranged structurally to form a different
functional groups.

▪ Physical properties are always different.

49

Structural Isomers
▪ Beginning with prefix but- there is more than
one way of combining C and H atoms.

Butane
Straight chain 2-methylpropane
Branched structure 50
 Isomers
▪ Draw all possible isomers of pentane, the first
isomer is always the straight chain:

51

Isomers
▪ Draw all possible structures of hexane.

52
 Isomers
▪ Isomers may differ in functional groups.
▪ Functional groups are the reactive parts of the
molecules and commonly contain elements such as
oxygen and nitrogen.
▪ In the alkene and alkyne homologous series, the C-
C double and triple bonds make up the functional
groups of the series.

53

Isomers: Examples involving class of

compound and functional Groups
Aldehyde: Ketone (carbonyl):
Propanal Popanone
CH3CH2CHO CH3COCH3

Carboxylic acid (carboxyl): Ester:

Propanoic acid Methyl ethanoate
CH3CH2COOH CH3COOCH3

54

#M10_CHE_SB_IBDIP_9755X LM1O_CHE_SB_IBDIP_9755X NewTab X

- ©file:///C:/Users/maaglan/Downloads/M10_CHE_SB_IBDIP_9755_U10_sec.pdf
class,whichreferstothetypeofcompound,andfunctionalgroup,whichreferstothesite
ofreactivityinthemolecule.
 ofreactivityinthemolecule.

Functional Class
Functional
group
Nameof
functionalgroup
Suffixin
IUPAC Exampleofcompound
General
formula

Groups:
alkane C,H.ethane CAH2042
alkene alkenyl H2C=CH2,ethene CaH2n

determine alkune

alcohol _OH
alkynyl

hydroxyl
-yne

-anol
HC==CH,ethyne

C›H§OH,ethanol

properties of
ether R-O-R' ether -oxyalkane H§C-O-C¿Hs,methoxyethane R-O-R'
aldehyde aldehyde(carbonyl) -anal C2HsCHO,propanal R-CHO

molecule R-CO-R'
ketone carbonyl CHCOCHa,propanone
C=0

carboxylic carboxyl -anoicacid C›HsCOOH,propanoicacid

acid

O-H
ester* ester -anoate C›H§COOCH;,methyl R-COO--R'
propanoate

0-R

amide carboxyamide -anamide C›H§CONH,,propanamide

amine -NH2 -anamine

C2H§NH2,ethanamine
nitrile •CEN nitrile -anenitrile C,HCN,propanenitrile
gene phenyl -benzene CgHSCHa,methylbenzene

C6H5.
Estersformwhenthealkylgroupofanalcoholreplacesthehydrogenofacarboxylicacidinacondensationreaction:
R-COOH+R'OH->R-COO-R'+HO

iforganic2.ppt alkenes.pdf

Class: Halides (Halogenalkanes)

▪ Halogen substituents (halides).
▪ The more halogens present in an organic compound
the greater the intermolecular forces due to
increased polarity.

▪ Explain why halogenated compounds dissolve in water,

while hydrocarbons do not?

56
 Halides
▪ Draw the structure:
▪ 2-fluoropropane

▪ 2-fluoro-2,4,4-trimethylpentane

57

Class: Alcohols
• Organic compounds containing the functional group –
OH group (hydroxyl).
1. When using the IUPAC system, the ending of the parent
alkane name ends in –ol.

2. The longest chain of C atoms must include the hydroxyl

group.

3. The position of the –OH group is given the lowest possible

number.
▪ Ex. CH3OH methanol

58
 Alcohols
Primary alcohol: 1°
The C attached to the
OH has 1 R group *R is any C
attached to it. containing group

Secondary alcohol : 2° Tertiary alcohol: 3°

2 R groups 3 R groups
attached. Attached.

59

Alcohols
• Primary alcohol
Ex. Ethanol

• Secondary alcohol Ex. Propan-2-ol (or 2-propanol)

60
 Alcohols
• Tertiary alcohol
Ex. 2-methylpropan-2-ol (or 2-methyl-2-propanol)

61

Class: Aldehydes
▪ C of the carbonyl group (C=O) MUST
be attached to AT LEAST one H.
General structure:
*R represents a C chain or H
▪ Naming: Use # of C prefix & ending –anal
▪ Ex. Carbonyl group

CH H
Methanal 3 Ethanal
HCHO CH3CH
Name and condensed structure? O
62
 Class: Ketones
▪ Contain the functional group carbonyl, which is a
C=O joined to two other carbon atoms (Must have at
least 3 carbons to be a ketone).
▪ Naming: Use # of C prefix & ending –one.
▪ Indicate # of C that contains the carbonyl group

Carbonyl group

CH3

General structure – R
Propanone
must be C groups CH3COCH
3 63

Aldehydes & Ketones

Draw, name and state the strongest type of
intermolecular force:
CH3CH2COCH3

CH3CH2CH2CHO

2-pentanone

propanal

64
 Class: Organic Acids
▪ A carboxylic acid is a compound with a carboxyl
group, which consists of a hydroxyl group (–OH) and
a carbonyl group (C=O).

–COOH

▪ R represent a carbon chain or H.

▪ Carboxylic acids are weak acids (ethanoic acid or
acetic acid).

65

Naming Carboxylic Acids

▪ Ex. Ethanoic acid:

▪ Name the following acids:

▪ CH3CH2COOH Propanoic acid
▪ CH3(CH2)4COOH Hexanoic acid
▪ Pentanoic acid
CH3CH2CH2CH2COOH

66
 Class: Esters
▪ Pleasant and delicious organic compounds.
▪ Give fruits, and perfumes their characteristic aromas.
▪ Occur naturally and important in the manufacture of soap.

▪ General formula of an ester:

▪ -RCOOR
▪ Esters can be prepared from a carboxylic acid and an
alcohol.
▪ This reaction is called esterification.

67

Naming Esters
▪ The H of the -COOH has been replaced by an R
group from an alcohol.
▪ The R group that replaced the H ends with “yl”
and is written FIRST.
▪ The R group from the acid forms the parent
name and is written SECOND.
▪ Change acid ending “ic” to “ate”.

68
 Name the following Esters:
▪ Ex. CH3CH2COOCH3
acid part Group that
replaced H

Methyl propanoate

▪ Ex. CH3CH2CH2CH2COOCH2CH3
Ethyl pentanoate

69

Learning Check: Esterification

▪ Which alcohol reacts with CH3COOH to form
the ester methyl ethanoate?
1) CH3COOH
2) CH3COCH3
3) CH3OH
4) CH3OCH3
Note: The first part of the ester name is “methyl” which
comes from the alcohol, therefore the alcohol must be
methanol.
70
 Class: Ethers
▪ General formula:
▪ Example:

Name: methoxymethane
or dimethyl ether

▪ Draw ethoxyethane (diethyl ether)

71

Ethers
▪ Ethers are extremely flammable chemicals and one of
the first anesthetics.
▪ Anesthetics make people go to sleep, or go
unconscious during surgery.
▪ Ethers are generally colorless, sweet-smelling
liquids at room temperature. They have a low
boiling point compared to water. Due to the
structure of the molecule, ether is extremely
flammable, which is partially why it is no longer
used in medicine today.
72
 Class: Amines
▪ Amines are organic compounds containing nitrogen
(N) (found in many medicines and drugs).
▪ They are named according to the # of C atoms attached to
the N and given the ending –amine or amino group.

73

Class: Amines
▪ Amines are organic compounds containing nitrogen
(N) (found in many medicines and drugs).
▪ They are named according to the # of C atoms attached
to the N and given the ending –amine.

CH3 CH2 N H CH
3
H CH3 N CH3
Ethylamine Trimethylamine
Primary amine Tertiary amine
74
 Amines
▪ Amino acids are building blocks of proteins.
▪ Amino acids contain the carboxylic group (-
COOH) but also contain an amine group

2-aminopropanoic acid

75

Class: Carboxamides
▪ Amide (amido) groups differ from amines because they
contain a carbonyl group (C=O):

▪ Amide bonds (peptide bonds) exist when amino acids

combine to make a protein.
▪ Also found in some medicine and drugs.

▪ Ex. Propanamide

76
 Class: Nitriles
• General structure:

• -Cyano functional group

• Suffix: nitrile
• Example: ethanenitrile

77

78
 79

Hydrocarbon & Functional Group

Reactions
▪ Alkanes generally have low reactivity because the C-C
and C-H bonds in all alkanes are relatively strong.
▪ A lot of energy is required to break these bonds.
▪ Alkanes are known as saturated hydrocarbons.

▪ Alkanes are stable under most conditions.

▪ The C-C and C-H bonds are essentially non-polar and
do not react with common reactants.
▪ Hydrocarbons undergo COMBUSTION and all
combustion reactions are exothermic.
80
 Hydrocarbon Reactions
1. Ex. Alkane combustion:
• Complete combustion in the presence of excess
oxygen yields carbon dioxide and water
• Products are fully oxidized.
– Example alkane reaction:

C3H8 + 5O2 → 3CO2 + 4H2O

81

Incomplete Combustion
• When oxygen is in limited supply alkanes
undergo incomplete combustion. In this reaction
carbon monoxide (poisonous gas) is produced.
2C3H8 + 7O2 → 3CO + H2O
• Carbon monoxide is a toxin - it irreversibly combines with the
hemoglobin in the blood and prevents it from carrying oxygen.

• If very little oxygen is available, solid carbon will

be produced.
C3H8 + 2O2 → 3C + 4H2O
82
 Combustion: Environmental Impacts
▪ Other hydrocarbons undergo
combustion. As C:H ratio increases with
unsaturation, smokiness of flame
increases due to unburned carbon.
▪ The products of all these reactions
(burning of fossil fuels) have a
dangerous impact on environment.

▪ Unburned carbon is released into the air

and can have a direct effect on the
respiratory system.

▪ Carbon particulates acts as catalysts in

forming smog and may contribute to
global dimming (incoming sunlight is
reflected back to space and less reaches 83
Earth’s surface).

Substitution: Halogenation
▪ Alkanes undergo substitution (halogenation)
reactions.
▪ An H is REPLACED by a halogen.

+ Cl Cl + H Cl
chlorine hydrogen
chloride
methane chloromethane

▪ CH4 + Cl2 → CH3Cl + HCl

84
 Substitution: Halogenation
▪ Let’s look at substitution more closely:
▪ Halogen molecules are able to react if they are
split into separate atoms, known as free
radicals.
▪ Free radicals contain an unpaired electron, which is
very reactive.
▪ Radicals will lead to a chain reaction (a series of
steps), initiation, propagation and termination.

85

Substitution: Halogenation
▪ Initiation
▪ The bond between the chlorine atoms is broken in the presence
of ultraviolet light energy.
▪ This process is known as homolytic fission: the two electrons
of a covalent bond are split evenly between two atoms
resulting in 2 free-radicals that each have a single electron:
▪ Ex:

UV light
+

Curly arrows will be used to

show the movement of electrons 2
during the breaking of the bond 86
 Substitution: Halogenation
▪ Reaction Mechanism:
Propagation
▪ Ex. + CH4 CH3 + HCl

The methyl free radical that forms is very reactive and

reacts with another chlorine molecule. The process
repeats itself, this is known as a chain reaction.

▪ Ex. CH3 + Cl2 CH3Cl +

Chloromethane
is formed 87

88
 Substitution: Halogenation
▪
Termination
▪ This occurs when two radicals react together.
CH3 + CH3Cl
+ Cl2
CH3 + CH3 C2H6

89

Substitution: Halogenation
Propagation
If this reaction occurs with bromine (and
UV light)
the reaction can be followed by the
disappearance
of the red/brown bromine color and the
formation of
acidic fumes of hydrogen bromide. This
reaction is sometimes used to differentiate
between alkanes and alkenes.
https://www.youtube.com/watch?
v=JGS0KYYn8ME
90
 Alkene Reactions
• Alkenes are unsaturated hydrocarbons that contain at least
one carbon-carbon double bond.
• The presence of the double bond makes alkenes more
reactive than the corresponding saturated alkanes.
• The double bond consists of one sigma (direct orbital
overlap) and one pi bond (parallel overlap of orbitals) and is
the site of reactivity.
• Alkenes undergo addition reactions.

91

Addition
▪ Addition reactions include the addition of:
1. hydrogen (hydrogenation)
2. bromine (bromination)
3. hydrogen halides (like HBr)
4. water (hydration)

92
 Addition: Hydrogenation
Ni catalyst
150 °C
+ H2
*Finely divided
nickel catalyst

• CH3CHCH2 + H2 → CH3CH2CH3
Unsaturated saturated

This process is used in margarine industry: saturated fats have higher melting
points and are solid at room temp; however, there are health concerns related to
trans fats produced by partial hydrogenation. 93

Addition: Bromination

+ Br2

▪ CH3CHCH2 + Br2 → CH3CHBrCH2Br

propene 1,2-dibromopropane

dihalogenated alkane
*Reactions happen rapidly at room temp 94
 Test to Distinguish between
alkanes and alkenes
Bromine water test to distinguish:
•The brown color of bromine water is immediately decolorized
(changes to colorless). when added to an alkene (like 1-hexene).
When bromine water is added to an alkane (like hexane), there is no
color change that occurs.
C2H4(g) + Br2 (aq) C2H4Br2 (aq)
brown colorless
•Why? The bromine reacted with the double bond in the alkene
in an addition reaction.

•Alkanes are saturated and unable to undergo an addition

reaction with bromine.
95

Addition: Hydrogen Halides

+ HCl

CH2CH2 + HCl → CH3CH2Cl

ethene chloroethane

monohalogenated alkane

*Take place rapidly in solution at room temp. 96

Reactivity: HI>HBr>HCl
 Addition: With Water (Hydration)
▪ Hydration converts an alkene into an alcohol.
▪ Ethene is an important product formed during cracking
(refinery process) of oil.
▪ Ethanol is formed from the addition of steam to ethene.

H2O steam
H2SO4 or phosphoric acid
(concentrated)
as a catalyst
Heat
300 °C

ethene ethanol
97

Addition Polymerization
• Under certain conditions, alkenes (monomers) can
undergo addition reactions to form long chains of
polymers containing thousands of carbon atoms.
• Substituted alkenes can undergo polymerization as well.
– Examples: PVC (polyvinylchloride – most widely used
plastic).

– PTFE (Teflon, polytetrafluoroethene) used in “non-stick”

products like pots and pans.

98
 Addition Polymerization
Break double bond
and monomers join

Ethene Repeating unit

monomers join Polyethene
(first synthetic plastic)

99

Addition Polymerization

propene polypropene
monomers join Manufacturing of clothing-
thermal wear

100
 Addition Polymerization
Show the reaction of polymerization of
the monomer chloroethene, identifying
the repeating unit.

chloroethene Polychloroethene (PVC)

monomers common plastic - packaging,
electrical cable insulating

101

Learning Check:
State the type of polymerization reaction shown by the
alkene below.

addition

102
Learning Check:

Deduce the structure of the resulting polymer showing three

repeating units.
You do not have to
use brackets around
repeating
units

103

Summary of Alkene Reactions

104
 Applications
http://www.chemhume.co.uk/ASCHEM/Unit%202/C
h9%20Alkanes/Alkanes.htm

105

Alcohols: Combustion
▪ Like hydrocarbons, alcohols burn in oxygen to
form carbon dioxide and water and energy is
released.
▪ The burning of methanol:
2CH3OH (l) + 3O2(g) 2CO2(g) + 4H2O(g)

▪ What is methanol (naphtha) used for?

– Methanol is considered to be a potential candidate to replace
fuels based on crude oil.
106
 Alcohols: Oxidation
▪ Alcohols can be oxidized (loss of H atoms) to
other organic compounds.
▪ Most common oxidizing agent used to oxidize ethanol
is potassium dichromate (K2Cr2O7 or simply
dichromate ion Cr2O72-).
▪ When the reaction mixture is heated, in an acidified
dichromate solution, the color changes from bright
orange (Cr6+) to green (Cr3+). Chromium ions are
reduced.

107

108
 Alcohols: Oxidation
▪ Application:
▪ Crystals of K2Cr2O7 are present in a breathalyzer
test. If a person had a enough alcohol on the breath
the alcohol will get oxidized and chromium will get
reduced, hence a color change indicating the
presence of alcohol.

109

Primary Alcohols: Oxidation

▪ Primary alcohols are oxidized in a 2-step reaction.
1. First an aldehyde is formed.
2. Further oxidation leads to a carboxylic acid.

Cr2O72- Cr2O72-
/H+ /H+

heat heat
Primary alcohol reflux reflux
Carboxylic
Aldehyde
acid
Refluxing is a technique that
involves the cyclic evaporation
and condensation of a volatile
reaction mixture, preserving the
110
solvent as it does not evaporate.
 Distillation
▪ Distillation can be used to obtain the aldehyde
produced in the reaction.

▪ Aldehydes have a lower boiling point than alcohol or

carboxylic acid and can be collected using a distillation
apparatus.
▪ In order to get a good acid yield DO NOT distill – we
need the aldehyde to oxidize to form acid.
▪ Note: aldehydes do not have hydrogen bonding between
molecules so lower b.p.

111

Secondary Alcohols
▪ Secondary alcohols are oxidized to a ketone by a
similar process:

2-propanol propanone
No further oxidation is possible
at this point as the carbon atom
of the functional group has no
hydrogens
attached to it. 112
 Tertiary Alcohols
▪ Tertiary alcohols ARE NOT readily oxidized.
▪ Too much energy is required to break bonds in a
tertiary structure.

X
NO reaction
2-methyl-2-propanol
Tertiary alcohol
113

114
 Condensation Reaction (Esterification)

H2SO4 catalyst
+ R- + H2O
OH (conc)
carboxylic acid ester water
alcohol
• Esterification is a reversible reaction (concentrated sulfuric acid is needed as a
catalyst to speed up the forward reaction).
– Most esters have a pleasant, fruity smell and are used both as natural and
artificial flavoring agents in food.

– Esters are also used as solvents in perfumes and plasticizers (substances used
to modify the properties of polymers by making them more flexible).
– Esters have lowest boiling point of substances in reaction and can be
separated by distillation
115

Condensation Reaction (Esterification)

116
 Learning Check: Esterification
▪ Which alcohol reacts with CH3CH2COOH to
form the ester methyl propanoate?
1) HCOOH
2) CH3CH2CH2OH
3) CH3OH
4) CH3OCH3

117

Condensation Reaction (Esterification)

Application Chemmatters and fuse

▪ https://www.youtube.com/watch?v=EJud8MKrvBE
▪ https://www.youtube.com/watch?v=ecHKrd7hn4U

118
 Halogenalkanes
• General Formula: CnH2n+1X
• Examples: CH3Cl C3H7Br
• The carbon-halogen bond is polar, making
halogenalkanes more reactive than alkanes.
– Halogens have a greater electronegativity than
carbon.

• The halogen acquires a partial negative charge and the

carbon acquires a partial positive charge (carbon
becomes electron deficient).
119

Halogenalkanes
• This makes carbon have the ability to attract
chemicals called nucleophiles – species which
are rich in electrons and attracted to regions of
molecules that are electron deficient.
• Halogenalkanes are saturated and undergo
substitution reactions.
• Nucleophiles are attracted to the electron
deficient carbon, leading to the substitution of
the halogen (nucleophilic substitution).

120
 Halogenalkanes
• OH- (from a basic solution) can substitute the
halogen converting the halogenalkanes to an alcohol
(nucleophilic substitution).

• Why is the hydroxide ion a good nucleophile?

– The hydroxide ion, OH- has a negative charge and
can attract the partially positive carbon bonded to
the halogen.
121

Type of Mechanism
• Halogenalkanes containing iodine are most
reactive because the C-I bond is not as strong as
C-F (the C-F bond is most polar so it is the
strongest and does not react easily).

122
 Type of Mechanism
• What part of the halogenalkane is the hydroxide ion
attracted to?
• Write the mechanism shown in the video (while you
not need to memorize the structural mechanism shown
with curly arrows you DO need to know that the
nucleophile is attracted to the partially positive carbon
atom and the conditions in which the reaction takes
place and the overall reaction shown at the end).
• Write down the second example.

123

Nucleophilic substitution reactions:

• Application link below:
• http://ozonewatch.gsfc.nasa.gov/facts/ozone.html

124
 Electrophilic Substitution
Alkenes undergo addition but benzene has resonance stability (delocalized
electrons) and generally undergoes substitution reactions rather than addition
reactions.

Electrophiles are reactants that are electron deficient (having a positive or

partial positive charge).
Electrophiles are attracted to the electron-rich benzene ring, leading to
electrophilic substitution reactions.
125

Electrophilic Substitution
• Electrophiles are attracted to the electron-rich benzene ring,
leading to electrophilic substitution reactions.

https://www.youtube.com/watch?v=klY4rldk7jc

126
 127

Spectroscopic Identification of Organic

Compounds
• Nature of Science: Improvements in
instrumentation – mass spectrometry (MS),
proton nuclear magnetic resonance (NMR) and
infrared spectroscopy (IR) have made
identification and structural determination of
compounds routine.

128
 Degree of Unsaturation or Index of
Hydrogen Deficiency (IHD)
• The degree of unsaturation or index of hydrogen
deficiency (IHD) can be used to determine from a
molecular formula the number of rings or multiple bonds
in a molecule.

• The degree of unsaturation is used to calculate the

number of rings and pi bonds (bonds that account for one
of the bonds in a double bond and two of the bonds in a
triple bond).

129

Degree of Unsaturation or Index of

Hydrogen Deficiency (IHD)
• A double bond = 1 degree of unsaturation
• A triple bond = 2 degrees of unsaturation
• A ring = 1 degree of unsaturation
• An aromatic ring = 4 degrees of unsaturation

• IHD can be worked out from the structure and from the
molecular formula.

130
 Degree of Unsaturation or Index of
Hydrogen Deficiency (IHD)
• From the structure: # of rings, double
and triple bonds IHD
Benzene 1 ring
3 double bonds
1 ring
cyclopentadiene
2 double bonds
cyclobutane
1 ring
ethyne

aspirin
1 triple bond

1 ring
5 double bonds
131

• From the molecular formula

• General formula: CcHhNnOoXx (x represents a
halogen)
IHD = (0.5)(2c + 2 – h – x + n):
• For ex:
C4H8O2 IHD = (0.5)(8 + 2 – 8) =
c=4
h=8 Therefore, the molecule contains either 1
double bond or 1 ring. There could be
n=0
several isomers.
o=2
x=0
132
• From the molecular formula
• General formula: CcHhNnOoXx (x represents a
halogen)
IHD = (0.5)(2c + 2 – h – x + n):
• Learning Check: IHD
C17H21NO4
C27H46O
C6H7N
C15H10ClN3O3

133

Proton Nuclear Magnetic Resonance

1H NMR Spectroscopy
How does it work?
• The atomic nuclei of hydrogen atoms can behave as tiny
magnets, that is, have two possible spin states (much like
a compass magnet, which aligns with the Earth’s
magnetic field).
• Nuclei spin in random directions, however, when an
external magnetic field is present, the nuclei align
themselves either with or against the field of the external
magnet.

134
 Proton Nuclear Magnetic Resonance
1H NMR Spectroscopy
How does it work?
• When nuclei align with applied field they have lower energy than
those against the field.

• By applying radio frequency it is possible to excite nuclei in low

spin states to high spin states – when the energy applied equals the
energy gap between the spin states then energy is absorbed by the
nuclei and are said to be in “resonance”.

• NMR spectra show signals, which represents energy absorbed by

sample and depends on chemical environment.

135

Proton Nuclear Magnetic Resonance

1H NMR Spectroscopy
APPLICATION:
• An important application of 1H NMR Spectroscopy is
associated with the fact that protons in water molecules
within human cells can be detected by magnetic
resonance imaging (MRI), which gives a 3D view of
organs in the human body.

136
 1H NMR Data: Data Booklet Page 26+27
Tetramethylsilane,
(CH3)4Si, (TMS), is
used a the reference
compound. It is an inert
molecule and assigned
0.00 ppm by definition.

All 12 H’s in TMS are

in exactly same
environment, which
produce one single
reference peak.

137

Protons in electron dense

environments are more
shielded by large electron
density surrounding them, and
therefore, will require a lower
frequency to induce transition
between nuclei spin states.

Protons are shielded more and

will feel applied magnetic field
less, which leads to a lower
shift. Shield (Upfield).

Deshield Shield
Downfield Upfield

138
 Protons near highly
electronegative
elements are considered
to be in electron poor
environments.

Electronegative
elements pull electron density
away from protons.

Protons are shielded less and

will feel applied magnetic field
more, which leads to a higher
shift. Deshield (downfield)

Deshield Shield
Downfield Upfield

139

Proton Nuclear Magnetic Resonance

1H NMR Spectroscopy
Number of Signals:
•Chemically Equivalent Protons are protons that are in the same
environment, and they must be identical in every way.
– Each group of chemically equivalent protons gives rise to a
signal.
– Different peaks are produced because nuclei that are not
in identical structural environments will not experience
the external magnetic field to the same extent.

•We can determine how many sets of equivalent protons there

are in a molecule by looking at the number of signals in its H-
NMR spectrum.
140
 Chemical Environment
• Example (2-propanol):
(A)

(C) (C)

(B)

141

Proton Nuclear Magnetic Resonance

1H NMR Spectroscopy
Integration Trace:
• Shows the relative number of hydrogen atoms present.
• The area under each signal is proportional to the amount
of radio energy and number of equivalent protons that
give rise to that signal.
– The numbers do not always correspond to the exact or absolute
number of protons. Instead, it tells us the relative number or
ratio of the amount of equivalent protons.

142
 Chemical Environment
• Example (2-propanol):
Integration Trace: 1:1:6
(A)

(C) (C)

(B)
143

1H NMR Spectrum: 2-propanol

Shift ppm
A: 4.008
B: 2.16
C: 1.200

Let’s look at our

Data booklet –
26+27

(A)
(C) (C)
3 peaks for these 3 different H
environments in spectrum
(B) 144
 1H NMR Spectrum: 1-propanol

(C) (A)
(d)

(B)

Shift(ppm)
3.58(A) 2.26(B) 1.57(C) 0.94(D)
145

1H NMR Spectrum: ethanol

(A)
(C) (B)

(C)

Shift(ppm)
A 3.687 B 2.61 C 1.226
146
 1H NMR Spectroscopy
• EdPuzzle Video
• Take all notes: (when you get to the quick questions you
can stop or you choose to do them if you want more
pracitce)
• https://www.youtube.com/watch?
v=LBHXbh3unBs&index=11&list=PL816Qsrt2Os1q
2OTlXPVbZvO4XmWZfLId

147

Predict the number of peaks and integration

ratio
Methyl ethanoate

148
 Proton Nuclear Magnetic Resonance
1H NMR Spectroscopy
3-pentanone

149

NMR Spectra

• https://www.youtube.com/watch?v=XIWc9eT476c
• https://www.youtube.com/watch?
annotation_id=annotation_531806421&feature=iv&
src_vid=JThK57u2lYo&v=tSFAqchZQ7g

• https://www.youtube.com/watch?
v=Y4BRFobuLro&index=13&list=PL816Qsrt2Os1q2
OTlXPVbZvO4XmWZfLId

• http://www.chemguide.co.uk/analysis/masspec/frag
ment.html#top 150

• http://www.chemguide.co.uk/analysis/ir/background.
 NMR Spectra

• https://www.youtube.com/watch?v=XIWc9eT476c

151

Mass Spectrometry (MS)

• In topic 2 we talked about principles of mass spectrometry.
When a gaseous molecule is ionized its molecular ion, M+,
(parent ion) is formed.
• The molecular ion peak in a mass spectrum, corresponds to
the molecular mass of the compound.
• The ionization process involved in the mass spectrometer
breaks up the molecule into smaller fragments (called
fragmentation).
– % abundance on fragments is on y-axis in spectrum. The x axis
represents the mass to charge ratio of the ion (m/z).

152
 Mass Spectrometry (MS)
• The fragmentation pattern observed in a mass spectrum
provides information on certain functional groups present in
a molecule.
– Section 28 of data booklet lists some fragments and their masses.
Some examples:
• [Mr – 15]+ results from the loss of –CH3
• [Mr – 17]+ results from the loss of –OH
• [Mr – 29]+ results from the loss of –CHO or – CH2CH3
• [Mr – 31]+ results from the loss of –OCH3
• [Mr – 45]+results from the loss of –COOH

153

Mass Spectrum The tallest line, (in this

case at m/z = 43) is called
Ex. Pentane the base peak.

43 The base peak is the tallest

Base peak peak because it represents
the most common fragment
ion to be formed - either
because there are several
ways in which it could be
produced during
M+ ion fragmentation of the parent
29 57 72 ion, or because it is a
particularly stable ion.

Different peaks represent different fragments of

molecule
154
Mass Spectrum M+ ion:
Ex. Pentane [CH3CH2CH2CH2CH3]+
43
Base peak

M+ ion
29 57 72

(57) Fragments: [CH3CH2CH2CH2]+ 72-57 = 15 (loss of methyl)

(43) [CH3CH2CH2]+ 72-29 = 43 (loss of ethyl)
(29) [CH3CH2]+ m/z is typical of ethyl ion 72-43 = 29
155

Mass Spectrum for Ethanoic Acid

43
45
Loss of
OH
60

Loss of
Fragment methyl What is the mass of
of methyl Ethyl or the molecular ion?
15 aldehyde
29 60

156
 Mass Spectrometry (MS)

•https://www.youtube.com/watch?v=XIWc9eT476c

157

Infrared Spectroscopy (IR)

• The basis of IR spectroscopy is the spring model.
• Every covalent bond is considered as a spring.
• Such a spring can be stretched, bent or twisted. A force is
required to cause the vibration.
– Light atoms vibrate at higher frequencies and heavier
at lower frequencies.
– The stronger the bond the more energy required to
stretch the bond.
 Infrared Spectroscopy (IR)
• Example: Modes of vibration of the water molecule

• Symmetric stretch

• Asymmetric stretch

• Symmetric bend

Infrared Spectroscopy (IR)

• Different molecules can absorb at different frequencies
because the energy required to cause a vibration will
depend on the bond enthalpy.
• The absorbance can be related to the transmittance in an
IR spectrum.
• The spectrum shows %T versus wavenumbers (cm-1).
• In an IR spectrum, functional groups can be identified.
 Infrared Spectroscopy (IR)
• The energy of IR radiation is weaker than that of visible and
ultraviolet radiation, and so the type of radiation produced is
different. Absorption of IR radiation is typical of molecular
species that have a small energy difference between the
rotational and vibrational states.
– A criterion for IR absorption is a net change in dipole moment in a
molecule as it vibrates or rotates. Using the molecule HBr as an
example, the charge distribution between hydrogen and bromine is not
evenly distributed since bromine is more electronegative than
hydrogen and has a higher electron density.

Infrared Spectroscopy (IR)

• HBr thus has a large dipole moment and is thus polar. The
dipole moment is determined by the magnitude of the charge
difference and the distance between the two centers of
charge. As the molecule vibrates, there is a fluctuation in its
dipole moment; this causes a field that interacts with the
electric field associated with radiation.
– If there is a match in frequency of the radiation and the natural
vibration of the molecule, absorption occurs and this alters the
amplitude of the molecular vibration. This also occurs when the
rotation of asymmetric molecules around their centers results in a
dipole moment change, which permits interaction with the radiation
field.
• http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Sp
ectroscopy/Vibrational_Spectroscopy/Infrared_Spectros
copy/Infrared%3A_Theory

• http://www.rsc.org/learn-
 Infrared Spectroscopy (IR)
• http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Sp
ectroscopy/Vibrational_Spectroscopy/Infrared_Spectros
copy/Infrared%3A_Theory

• http://www.rsc.org/learn-
chemistry/collections/spectroscopy/introduction#IRSpec
troscopy

Infrared Spectroscopy (IR)

• In order for a covalent bond to absorb IR radiation there
must be a change in the molecule dipole moment
associated with the vibration mode.
• Nonpolar molecules like diatomic molecules are
nonpolar and IR inactive.
– However, CO2 is IR active for asymmetric stretch or
symmetric bend because a dipole moment is induced.

Symmetric stretch Asymmetric stretch

IR inactive IR Active

Symmetric bend
IR Active
 Infrared Spectroscopy (IR)
• The characteristic ranges for the IR absorptions of
various bonds in difference classes of molecules and of
functional groups are given in section 26 of the data
booklet.
• Note the following absorptions:
• Strong broad peak in the range of 2500-3000 cm-1
– Characteristic of O-H bond
• Strong broad peak in the range of 1700-1750 cm-1
– Characteristic of C=O bond
• Strong broad peak in the range of 2850 - 3090 cm-1
– Characteristic of C-H bond

Ethanol IR Spectrum

Fingerprint region: usually

between 300-1400 cm-1
(more complex vibrations can
be identified in this region
and different for different
molecules).
 Ethanal IR Spectrum

Strong IR absorption in the Strong IR absorption in the

wavenumber range 1700-
1750 cm-1, which suggests
the presence of C=O bond
(look at data booklet section
26).
wavenumber range 2850-
3090 cm-1, which suggests
the presence of C-H bonds
(look at data booklet section
26).

Propanal IR Spectrum

Identify strong peaks in IR

spectrum and determine the number
of different proton environment's in
the chemical structure.
 C3H6O2 IR Spectrum

2850-3090 cm-1 Probably

Broad absorptionSuggests C-H not cyclic
3000 cm-1 bond given the
Strong absorption 1700
Suggests O-H cm-1 strong
bond Suggests C=O bond C=O peak

Calculate the IHD for this molecule. IHD= 1

Identify strong peaks in IR spectrum. could mean 1 ring
or 1 double bond

C3H6O2 NMR Spectrum

Suggests -COOH group

Determine the number of different

proton environment's in the chemical
structure.
3
 C3H6O2 MS Spectrum

If the Mass spectrum shows a peak with m/z = 45, what could
this suggest? (use your data booklet)
-
COOH
Deduce the structure of X.

Propanoic acid